Certain dicarboxy acid esters of oxyalkylated polymerized hydroxyamines



Patented Nov. 4, 1947 CERTAIN DICARBOXY ACID ESTERS OF OXYALKYLATEDPOLYMERIZED HY- DROXYAMINES Melvin De Groote, University City, andBernhard Keiser, Webster Groves, M0,,

assignors to Petrolite Corporation, Ltd., Wilmington, DeL, a corporationof Delaware No Drawing. Original Eapplication April 2, 1945,

Serial No. 586,264. Divided and this application November 26, 1945,Serial No. 630,971

8 Claims. (01. 2e0 404.5)

This invention relates to a new chemical compound or product, ourpresent application being a division of our pending application SerialNo. 586,264, filed April 2, 1945.

The object of our invention is to provide a new material or compositionof matter, that is particularly adapted for use as a demulsifier in theresolution of crude oil emulsions, but which is also capable of use forvarious other purposes, or in various other arts.

The new material or composition of matter herein described, consists ofan ester derived by esterification reaction between (a) An oxyalkylatedheat-polymerized triethanolamine, or the like; and

(1)) Certain dicarboxy acids hereinafter described.

It is well known that aminoalcohols, particularly tertiaryaminoalcohols, react with high molal acids, such as higher fatty acidsor their equivalents, to yield esters having basic properties providedthat there is no negative group such as an acyl radical or aryl radicaldirectly attached to the amino nitrogen atom. For instance, the reactioninvolving diethyl ethanolamine and stearic acid may be shown in thefollowing manner:

CzHt nooiojf jfjgfgoolnm CizHa If, however, triethanolamine issubstituted for diethylethanolamine, the same comparable reaction isillustrated in thefollowing manner:

7 02114011 RC 91111353} 0 0mm C2H4OH The reaction is generally conductedat fairly high temperatures, for instance, temperatures sufiicient todrive on water yet below the point of pyrolysis, for example, 150 to 250C. Under such conditions, the use of triethanolamine, or a similarpolyhydroxylated reactant, may involve etherification, as well asesterification. Thus, it frequently happens that such a reaction orseries of reactions, when triethanolamine or the like is used, may notbe quite as simple as above indicated.

The dicarboxy acids herein contemplated as reactants or theirequivalents, such as their ethyl or methyl esters, are obtained, bythepolymerization, and principally, the dimerization of esters ofunsaturated fatty acids, particularly conjugated diethylenic acids. Suchdimerized acids or their esters are well known compositions and havebeen used for various processes, such as the manufacture of a resinousor synthetic coating material sold under the descriptive name ofNorelac, which, in turn, is obtained by reaction between such dimerizedcompounds and certain diamines. (See Oil and Soap, volume 21, No. 4,page 101.)

The chemistry of polymerization has been discussed in the literature,but for convenience, reference is made to U. S. Patent No. 2,347,562,dated April 25, 1944, to Johnson, where the following appears:

1(a) 2OH (CH2)5(CH=CH)2(CH2) fi0 on,

2 moles methyl ester 9,1l-octadecadienic acid (originally present and/0rformed by isomerizationol 9,12 isomer) ((IJH2)1EIJO CH3 As to thepreparation of such polymerized acids or esters, it is to be noted thatany polyene fatty acid or its ester may be employed as a raw material.In fact, one may use a mixture such as one which occurs naturally invarious drying oils. The most important of these are the octadecadienicor octadecatrienic fatty acids or their esters, but the polymeric fattyacids containing 20, 22 and 24 carbon atoms found in fish oils are alsosuitable.

Examples of the polyene fatty acids, the esters of which arepolymerized, are the following: 9,11- and/or 9,12-octadecadienic acids(obtainable from perilla o'il, linseed oil and other drying oils) bothalphaand betaeleostearic acids (obtainable from tung oil), etc.

Ordinarily speaking, polymerization is conducted so as to obtain acomparatively high conversion from the monomeric state to the polymericstate, even though some polymers higher than the dimeric state may beproduced, for instance, trimers or tetrainers. If desired, such polymerscan be separated from each other, insofar that the dimers can beseparated from the higher polymers, such as the trimers or tetramers.The method employed involves selective solvent action, but does notrequire further description, for the reason that there is no objectionto the moderate presence of higher polymers along with the dimers hereincontemplated for reaction, and if polymerization is conducted undercomparatively mild conditions so as to polymerize not over fifty percentof the polyene acid esters, then and in that event, the product obtainedis principally the dimeric product. In any event, this is immaterial,for the reason that the dimeric products, either in the form of theethyl or methyl ester or the acids themselves, may be purchased in theopen market at the present time.

It may be Well, however, to indicate briefly the general conditions ofpolymerization. If methyl or ethyl esters of the polyene acids beutilized, it has been found that temperatures between about 250 C. andabout 350 C. are suitable for the polymerization. The time required forthis polymerization varies not only with the temperature, but with theacid and the particular ester which is used. Generally, a period of fromabout one-half hour to about 50 hours is suitable, and in mostinstances, the polymerization may be effected in not over 12 hours.Dimerization can usually be accomplished in approximately one-half thisperiod of time. If a conjugated unsaturated ester, such as the methylester of eleostearic acid be employed, a suificient degree ofpolymerization may be obtained within onehalf to one hour at about 300C., whereas, the methyl linolenates and linoleates generally requirefrom about 5 to 12 hours or more. To

speed up the polymerization process, suitable catalysts may be added,examples of which are: fullers earth (preferably acid-treated) bentonite(preferably acid-treated), stannic chloride, etc. If catalysts beemployed, it is sometimes possible to use lower temperatures and shorterperiods of time, or shorter periods of time, than those indicated above.

In general, it is preferred to conduct the polymerization in an inertatmosphere of carbon dioxide, nitrogen or other inert gas. merization ispreferably continued until the refractive index, density and averagemolecular weight approach constant values. At this point, thepolymerized esters are separated from the unpolymerized esters by anysuitable method. In subsequent examples, there is suggested theseparation of these esters by distilling oil the unpolymerized esters atan absolute pressure of about 1-5 mm. of mercury and at temperatures upto about 300 C. Another way in which this separation may be effected, isby extraction with methanol or other suitable solvent. Generally, theresult of polymerizing yields about 30% to 75% of the polymeric esters.As indicated previously, if the reaction is conducted so as to obtainmild polymerization, and less than 50% of the product in the polymericstate, it will be found that the bulk, if not all, are readilyobtainable in the dimeric state.

Previous attention has been directed to t e f ct The polythat the estersof any polyene higher fatty acid may be employed, or mixtures thereof.Polymerization of the kind indicated is concerned largely withconjugated polyene structure. Previous reference has been made to suchacid esters as show such structure. However, the fact that any polyeneester may be employed as a raw material for the manufacture of theherein contemplated reactants, is due to the fact that such materialscan be isomerized to the conjugated structure. It is well known thatalkali metal hydroxides act on conjugated fatty acid and oils in eitheraqueous or alcoholic solutions. Procedures are available which enablethe conversion of 30% to 50% of conjugated acids from soyabean andlinseed oils. See Industrial and Engineering Chemistry, volume 34, page237, and U. S. Patent No. 2,350,583, dated June 6, 1944, to Bradley.Thus, the raw materials herein contemplated include, among others, theisomerized fatty acids, or esters obtained from unsaturated higher fattyacids having at least two nonconjugated double bonds. Such materials areobtainable, for example, from linseed oil, soyabean oil, perilla oil,poppyseed o-il, cottonseed oil, sunfiowerseed oil, and a number of fishoils. The fatty acids, prior to isomerization, generally have an iodinenumber of 110, or substantially higher.

A further description of polymeric fatty acids and their compounds isfound in U. S. Patent No, 2,357,839, dated September 12, 1944, to Manley& Evans. Note that in said patent such acid is referred to as apolymeric fat acid. By analogy the dimeric acid would be referred to asdimeric fat acid.

From a practical standpoint, two other facts are of marked interest.There is now available a solvent treated dehydrated castor oil or fattyacid derivative in which the 9,11 isomer is present to the extent ofapproximately 85%. This commercial product is particularly desirable asa reactant for preparation of the herein contemplated compounds. Anotherfactor of interest is recognition of the effectiveness of certaincatalysts in converting non-conjugated unsaturated fatty oils or acidsso as to result in the conjugated isomer. For instance, see Oil 8; Soap,volume 21, No. 11, page 329.

POLYMERIZED ESTER Example 1 800 parts of the methyl esters of tung oilfatty acids are heated, preferably in an atmosphere of carbon dioxide orother inert gas, to a temperature of about 275 C. in approximately 40minutes, and the temperature is maintained at this point for aboutone-half an hour. The relatively volatile and unpolymerized esters areremoved by distillation at about 1-5 mm. of mercury absolute pressure,the temperature being gradually raised to about 300 C., leaving aresidue containing 365-380 parts of non-volatile polymerized esters.

POLYMERIZED ESTER Exam'pZe 2 1000 parts of the methyl esters of thefatty acids of a solvent treated dehydrated castor oil, the majorproportion, for instance, to of which contains the methyl ester of 9,11-and 9,12-octadecadienic acid, are polymerized at 300 C. for about 3hours in an inert atmosphere. The Volatile and unpolymerized esters arer moved by distillation at 1-5 mm. of mercury absolute pressure,thetemperature being gradually raised to about 300 C., leaving as aresidue about 450-460 parts of non-volatile polymerized esters.

POLYMERIZED ESTER Example 3 2000 parts of the methyl esters of the fattyacids of soyabean oil are mixed with 200 parts of activated bentonite(Super-Filtrol) and the mixture is heated, preferably in an inertatmosphere at about 280 C. for about one-half an hour. The product isfiltered and the volatile and unpolymerized esters are removed bydistillation at 1-5 mm. of mercury absolute pressure, the temperaturebeing gradually raised to about 300 C., leaving as a residue about835-840 parts of polymerized esters.

The second class of reactants employed in the manufacture of thecompounds, used for example, as demulsifiers in the demulsification ofpetroleum emulsions, consist of oxyalkylated surface-activeheat-polymerized aminoalcohols, which, in monomeric form, are secondaryor tertiary amines containing at least two alkanol or hydroxyalkylradicals.

Briefly stated, such compounds may be obtained by the polymerizationoftriethanolamine, tripropanolamine, or the like, in such a manner as toeliminate water and produce ether linkages. Such polymers, consisting oftetramers or more highly polymerized forms, such as pentamers, hexamers,etc., and including decamers, or even more highly polymeriZed forms, arecharacterized by showing surface-activity. This means their dilutesolutions have the ability to cause foam, to reduce the surface tensionof water, to act as emulsifiers, etc. The exact composition cannot bedepicted by the usual chemical formulae, for the reason that thestructures may be cyclic or acyclic, or both, and subject to widevariations. The primary reaction is unquestionably etherization,although if some secondary amine, as, for example, diethanolamine,dipropanolamine, or the like, is present, it is barely possible thatwater is also eliminated to some degree by a reaction other thanetherization, with the result that two nitrogen atoms are united by analkylene radical, as distinguished from an alkyleneoxyalkylene radical.

Even though the exact structure of the surface-active heat-polymerizedalkanolamines herein contemplated is not fully understood, it is to benoted that their method of manufacture is well known and that they areused commer- 4 cially for various purposes. The hereinafter includeddescription is typical of the conventional polymers. The alkanolamineshaving a single nitrogen atom, i. e., monoamines, and particularly thosewhich represent secondary or tertiary amines, may be contemplated intheir simplest aspect as oxyalkylated derivatives of ammonia. Forexample, even though diethanolamine and triethanolamine may bemanufactured in various ways, such compounds can be manufactured bytreating one mole of ammonia with two or three moles of ethylene oxide.Analogs are prepared by the use of other alkylene oxides containing areactive ethylene oxide ring, as, for example, propylene oxide, butyleneoxide, glycide or methylglycide. Such products need not be deriveddirectly from ammonia, but may be derived from primary amines containingan aliphatic radical having 6 carbon atoms or less, as, for example,methylamine, ethylamine,

6 propylamine, butylamine, amylamine, and hexylamine.

It is to be noted that if a product like triethanolamine is treated withan excess of an oxyethylating agent, for instance, ethylene oxide, oneintroduces the oxyethylene radical between the terminal hydrogen atomand the adjacent oxygen atom. Thus, ether aminoalcohols obtained byreacting triethanolamine or tripropanolamine with one or two, or evenwith three to nine moles of ethylene oxide, are well known. The othersimilar etheraminoalcohols are derived in the same manner and require nofurther description. For purposes of clarity, the secondary or tertiaryamines herein contemplated as raw materials or reactants forpolymerization, may be summarized by the following formula:

[HOR.(0R).,.]..

N 1],. wherein OR is an alkylene oxide radical having 4 carbon atoms orless, and preferably, is the ethylene oxide radical. As indicated, ORmay be the propylene oxide radical, the butylene oxide radical, theglycide radical, or the methyl glycide radical; R1 is a member of theclass consisting of hydrogen atoms and alkyl radicals having 6 carbonatoms or less; m represents a numeral varying from 0 to 3; n representsthe numeral 2 or 3; and n represents the numeral 0 or 1, with theproviso that n plus 1!. equals 3.

Previous reference has been made to the fact that one may use asecondary or tertiary amine as a raw material. We prefer to use atertiary amine, and particularly a tertiary amine containing 3 alkanolradicals; more specifically, we particularly prefer to usetriethanolamine, and find that the commercially available product issuitable, in spite of the fact that it contains moderate amounts ofdiethanolamine, and possibly smaller amounts of monoethanolamine. It hasbeen previously pointed out that the amino hydrogen atoms, asdistinguished from the alcoholic hydrogen atom, may enter into thepolymerization reaction without afiecting the suitability of the finalpolymer. It will be pointed out subsequently that the temperaturesemployed for polymerization are, for instance, in the neighborhood of250 C.

This means that in most instances, monoethanolamine or diethanolamine,if present orig inally, may be volatilized and lost before anopportunity presents itself for polymerization. We have found nosignificant difference, for example, whether a, polymer has beenobtained from chemically pure triethanolamine substantially free fromdiethanolamine and monoethanolamine, or from commercial triethanolaminehaving minor percentages of the primary or secondary amine present.

In the examples hereinafter included, it is noted that the polymer mustrepresent the tetrameric stage, or a higher degree of polymerization,and must be surface-active in the conventional sense previously referredto. The products obtained in the manner herein described, whenmanufactured in iron vessels, represent viscous deep-ambercoloredproducts. The degree of polymerization can be estimated approximately inthe usual manner by loss of Water and increase in viscosity. However, itis better to make an actual molecular weight determination in the usualmanner. In any event, a determination which shows surfaceactivity meansthat the product is at least in the tetrameric state, and if the productis heated for some period of time after it has shown surfaceactivitywith further loss of water and with fur ther increase in viscosity,obviously the degree of polymerization, as far as the average polymergoes, must be beyond or higher than the trimeric state.

The polymerization of the basic hydroxy amines is affected by heatingsame at elevated temperatures, generally in the neighborhood of ZOO-270C., preferably in the presence of catalysts, such as sodium hydroxide,potassium hydroxide, sodium ethylate, sodium glycerate, or catalysts ofthe kind commonly employed in the manufacture of superglycerinated fatsand the like. The proportion of catalyst employed may vary from slightlyless than 0.1% in some instances, to slightly over 1% in otherinstances. Needless to say, in the event the alcoholamine islow-boiling, customary precautions must be taken so as not to lose partof the reactants. On the other hand, conditions must be such as topermit the removal of water formed during the process. At times theprocess can be conducted most readily by permitting part of the volatileconstituents to distil, and subsequently allowing the vapors tocondense. The condensed volatile distillate usually contains waterformed by reaction. The water can be separated from such condenseddistillate by any suitable means, for instance, distilling with Xylene,so as to carry over the water, and subsequently removing the Xylene. Thedried condensate is then returned to the reaction chamber for furtheruse. In some instances, condensation can best be conducted in thepresence of a high-boiling solvent, which is permitted to distil in sucha manner as to remove the water of reaction. In any event, the speed ofreaction and the character of the polymerized product depend not onlyupon the original reactants themselves, but also on the nature andamount of catalyst employed, on the temperature employed, the time ofreaction, and the speed of water removal, i. e., the effectiveness withwhich the water of reaction is removed from the combining mass.Polymerization can be effected Without the use of catalysts in themajority of instances, but such procedure is generally undesirable, dueto the fact that the reaction takes a prolonged period of time, andusually a, significantly high temperature. It is noted that in thesubsequent examples the final compositions of matter which arecontemplated are preferably polymerized hydroxylated tertiary amines.Thus, all the subsequent description of polymerized hydroxyamines hasbeen limited largely to the tertiary type, which is obviously thepreferred type. However, it must be recognized that polymerized hydroxyamines, particularly if polymerized for a fairly long period of time, ata fairly high temperature, and in the presence of an active catalyst,may result in a, polymerization reaction which ends in a product that iswaterinsoluble, or substantially water-insoluble. Obviously, suchwater-insoluble material can be obtained more readily from a more highlyhydroxylated amine than from a lower one.

The use of the word surface-active, as herein employed and as generallyused, refers to a compound which is water-soluble in the sense that itat least produces a colloidal sol or solution; thus, we do notcontemplate the use of products obtained by polymerization to the degreethat they are no longer soluble or miscible in water, except ashereafter specified.

Incidentally, it must also be recognized that the speed of reaction andthe degree of polymerization are commonly affected by the'nature of thevessel in which the reaction takes place. In the examples cited, it isintended that reaction take place in a metal vessel, such as iron.However, in order to obtain the-same degree of polymerization, whenconducting the reaction in a glass-lined vessel, it is quite likely thatthe period of reaction would have to be increased 400%.

Suitable amines have been previously indicated, but the following may benoted in addition: Propyl propanolamine, cyclohexyldiethanolamine,cyclohexyldipropanolamine, etc.

Other well known amines which may be employed are the following:

(See U, S. Patent No. 2,290,415, dated July 21, 1942, to De Groote.)

HEAT-POLYMERIZED HYDROXYAMINE Example 1 1% of caustic soda is added tocommercial triethanolamine and the product heated for approximately 3hours at 245-260" C. The mass is stirred constantly, and any distillateis condensed and reserved for re-use after an intermediate re-runningstep for purposes of dehydration. At the end of approximately 2%; to 3/2 hours, the molecular weight determination shows that the material islargely dimeric.

HEAT-POLYMERIZED HYDROXYAMINE Example 2 The same procedure is employedas in the previous example, except that heating is continued forapproximately another 1 /2 hours. In this instance, the reaction mass islargely a polymeric 9 material, with an average molecular weight rangeindicating the presence of approximately four to five nitrogen atoms inthe polymer.

HEAT-POLYMERIZED HYDROXYAMINE Example 3 HEAT-POLYMERIZED HYDROXYAMINEExample 4 Tri-isopropanolamine is substituted for triethanolamine inExamples 1, 2 and 3.

HEAT-POLYMERIZED HYDROXYAMINE Example 5 Tripentanolamine is substitutedfor triethanolamine in Examples 1, 2 and 3.

HEAT-POLYMERIZED HYDROXYAMINE Example 6 Polyethanolamine of thefollowing formula:

oiniowln onn is substituted for triethanolamine in the previousexamples.

The entire invention can be applied in an overwhelming majority ofinstances, if one has available only three types of heat-polymerizedcommercial triethanolamine. One type contemplates the polymerizationwhich approximates on the average the pentameric form, i. e., thetetrameric through the hexameric form. The second type represents thenext higher polymerization, which, in the bulk, approximates aheptameric state through the nonameric state. The third class representsin the bulk the decameric and. somewhat higher states through andincluding, for example, the dodecameric state. These three grades ortypes or varieties of polymers of commercial triethanolamine areeconomical in cost, easy to prepare, and really are the outstandingreagents for employment in the present process. It is to be noted thatExample 1, preceding, is concerned with the manufacture of a dimericform. This is included,for the reason that it is sometimes convenient toproduce the dimeric or trimeric form, and then subsequently, polymerizeto a degree showing a considerably increased molecular weight. Thus, attimes, such interrupted operation may show some convenience incomparison with a single polymerization step.

As previously stated, the raw material subjected to oxyalkylation, andparticularly oxyethylation, is a heat-polymerized, surface-active,water-soluble amine condensate, as described in detail previously.Wemuch prefer to use heatpolymerized condensation products derived fromcommercial triethanolamine. Furthermore, it must be remembered that thefinal criterion of the degree of polymerization; especially initialstate, is dependent upon anactual molecular to not over 200 pounds.

10 weight determination, or an equivalent test, rather than based simplyon time of reaction.

It is obvious that one cannot polymerize a material such asdiethylethanolamine and have a suitable material for subsequentoxyalkylation. One may, of course, employ a heat-polymerized productobtained from an admixture of reactants in which a compound such asdiethylethanolamine is one ingredient or reactant.

It is obvious that proper selection of reagents will invariably yield afinal product in which amino hydrogen atoms or hydroxyl radicals arepresent, i. e., a material susceptible to oxyalkylation. Indeed, ifthere is any doubt as to the suitability of a heat-polymerized product,it can be readily subjected to treatment with ethylene oxide in alaboratory autoclave and its reactivity noted. If it is not reactive toethylene oxide, it would not be a satisfactory reactant.

The treatment of amines, whether they be primary or secondary amines,with ethylene oxide, is well known. The eiTect of such reaction is toconvert such primary or secondary amines into tertiary amines having analkylol radical or its equivalent. Obviously, then a tertiary aminecontaining an alkylol group or its equivalent is readily susceptible tooxyalkylation. Briefly stated, such oxyalkylation of reactive amines,particularly when ethylene oxide is used as the oxyalkylating agent, canbe conducted under comparatively mild conditions, such as temperaturesof 125 C. to 200 C. under pressure of lbs. In using ethylene oxide, suchreaction is generally complete within three to five hours. When otheroxyalkylating agents are used, which are less reactive than ethyleneoxide, for instance, propylene oxide, more effective or drasticconditions of'reaction may be required, such as longer period ofreaction, increased temperature, increased pressure, etc.

As to suitable oxyalkylating agents, we particularly prefer to useethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

OXYALKYLATED POLYMERIZED HYDROXYAMINE Example 1 One pound mole of amaterial of the kind described under heading Polymerized hydroxyamine,Example 2, is treated with three pound moles of ethylene oxide at amaximum pressure of approximately pounds, and at a temperature ofapproximately C. until reaction is complete, as indicated bysubstantially complete absorption of ethylene oxide.

OXYALKYLA'IED POLYMERIZED HYDROXYAMINE Example 2 The same procedure isfollowed as in Example 1, immediately preceding, except that six poundmoles of ethylene oxide are employed for each pound mole ofheat-polymerized amine.

OXYALKYLATED POLYMERIZED HYDROXYAMINE Example 3 The same procedure isfollowed as in Example 2, immediately preceding, except that instead ofemploying six pound moles of ethylene oxide for reaction with one poundmole of the polymerized amine, one employs instead nine pound moles ofethylene oxide.

OX'YALKYLATED POLYMERIZED HYDROXYAMINE Example 4 The same procedure isfollowed as in immedisector OXYALKYLATED POLYMERIZED HYDROXYAMINEExample 5 The same procedure is followed as in Examples 1 to l,immediately preceding, except that propylene oxide is substituted forethylene oxide.

It will be noted that in the preceding examples no attempt has been madeto remove the alkaline catalyst which may generally be present duringthe heat-polymerization of the hydroxyamine, which catalyst appears toaccelerate oxyethylation.

The oxyalkylated and heat-polymerized triethanolamine or similarreactants have substantially the same appearance after oxyalkylation,particularly oxyethylation, as prior thereto, except that they are aptto be somewhat thinner and less resinous in character. The color isusually dark reddish or amber.

There is no need to change the dicarboxy acid esters to the acids. Onemay employ the methyl or ethyl esters for reaction with triethanolamine,heat polymerized triethanolamine or oxyethylated heat-polymerizedtriethanolamine. In such reaction a low molal alcohol, to wit, methyl orethyl alcohol, is eliminated instead of water. This may be shown in amanner comparable to a previous reaction in the following way:

iijffii iilfifl' ji saponification of the ethy1 and methyl ester,followed by acidification, yields the free acids. In some of thesubsequent reactions one need not necessarily unite both 'carboxylradicals with the amine radical. In other Words, the reaction can beconducted between the dicarboxy compound and the polyhydroxyla'ted amineso as to eliminate only one mole of water, or one mole of methyl alcoholcr'ethyl alcohol. We have found that the type or compoun wherein anycarboxyl radical'not esterified with an aminoalcohol group or "itsequivalenh'is in a free 'form, or unreacted form, yields abette'r'demulsifier than the corresponding esterrorm. The reasonprobably resides in the fact that the carboxyl may unite electrovalentlywith an amine which is part of the same molecule, thus forming an innersalt or a compound comparable thereto, or possibly with an amine residuewhich is part of another molecule, and thus, promote association. Thecorresponding 'es'ter radical would not participate in suchmodification.

AMINOESTER Example 1 Four separate batches of heat-polymerizedtriethanolamine corresponding, roughly, to a tetramer and manufacturedin a manner previously described under the heading Heat-polymerizedhydroxyamine, Example 2, are treated with approximately 3, 6, l and 15molecular proportions of ethylene oxide, Assuming the molecular weightof the tetramer'to be 675, one can conveniently treat four batches ofthe tetramer equal to 675 pounds each with 150, 300, 400 and 675 poundsof ethylene oxide. The result represents 12 825, 975, 1125 and 1350pounds of the oxyethylated derivative. 7

1 pound mole of a dimerized soybean fatty acid corresponding tothe'following formula:

and having a molecular weight of 560, is reacted in the conventionalmanner with 1 pound mole (825 lbs.) of the 1:3 oxyethylated derivativepreviously described. The reaction is conducted at approximately to 225for approximately 1 /2 to 2 hours, until 1 pound mole of water iseliminated. The reaction is conducted with constant stirring and withelimination of the Water of formation. The procedure is substantiallythe same as the esterification of triethanolamine with stearic acid. Thefinal product is a viscous amber product showing colloidal solubility inwater and better solubility in presence of dilute acid.

We prefer to conduct the esterification reaction at a temperature whichis distinctly lower than the temperature reaction employed inpolymerization of the triethanolamine or similar hydroxyamine, Thepurpose of such procedure is to promote esterification, rather than anyadditional etherization. Such procedure has the added advantage that bycollecting the water of esterification, one can estimate or measure theextent of esterification. If, however, etherization takes place at thesame time, there is the disadvantage that the water collected does notnecessarily represent water of esterification alone, but to some extent,represents water of etherization.

I AMINOESTER Example 2 The same procedure is employed as in thepreceding example, except that the time of heating is increased toapproximately 2 to 2 /2 hours, so as to eliminate 1%; pound moles ofwater.

AMINoEsrER Example 3 The same procedure is employed as in the precedingexamples, except that the time of heating is increased to approximately2% to '3 hours, so as to eliminate 2 pound'm'oles of water.

AMINOESTER Example 4 The same procedure is employed as in the precedingexamples, except that the time of heating is increased to approximately4 hours, so as to eliminate more than 2 pound moles of water, i. e., toinsure some additional etherization as well as esterification.

AMINOESTER Example '5 The same procedure is employed as in Examples 1 to4, preceding, except that the 1:6, 1:10 and 1:15 ratio oxyethylatedderivative is employed instead of the 1:3 ratio oxyethylated derivative..Thismeans that 9'75 pounds of the 1:6 ratio compound, 1125 pounds ofthe 1:1 0'ratio compound, and 1350 pounds of 1:15 ratio reof the same,etc.

places 825 pounds of the 1:3 ratio employed in The same procedure isfollowed as in Examples 1 to 5, inclusive, except that an oxyethylatedheptamer or equivalent is employed, Such product may be obtained by theoxyethylation of a product such as that described under the headingHeat-polymerized hydroxyamine, Example 3. If one employs 945 as anaverage molecular weight value, and then the same amounts of ethyleneoxide are added as in the previous example, 150 pounds, 300 pounds, 450pounds, and 657 pounds, the molecular weightsof the oxyethylatedproducts then approximate 1100, 1250, 1400 and 1625. In all otherrespects, the products areobtained in the same manner as in Example 5.

AMINOESTER Example 7 The same procedure is followed as in Example 5,preceding, except that one employs an oxyethylated decamer or theapproximate equivalent thereof. Using a value of 1325 for the molecularweight of the decamer, it means the same datio employed in Example 5,preceding, i. e., 1:3, 1:6, 1:10 and 1:15, giving oxyethylatedderivatives in which the molecular weights correspond to 1475, 1625,1775 and 2000. In all other respects, the products are obtained in thesame manner as in Example 5.

AMINOESTER Example 8 The dimerized acids obtained from tung oil fattyacids are employed instead of the corresponding derivative derived fromsoyabean oil fatty acids. Compare Polymerized ester, Example 1,preceding, with Polymerized ester, Example 3, preceding.

The amines contemplated for reaction with the dicarboxy acids arepolyamines having basic amino radicals. Thus, they can form hydrates bycontact with water or salts by combination with organic or inorganicacids, thus forming the acetate, hydroxyacetate, lactate, gluconate,propionate, caprate, phthalate, fumarate, maleate, benzoate, succinate,oxalate, tartrate, chloride, nitrate, or sulfate. The aminoester,without contact with water or acid, may of course, be dissolved in ananhydrous solvent.

We desire to point out that we are aware of the fact that there areother reactants, which,

at first glance, appear to bear a superficial relationship to thereactants herein contemplated. One might assume that such reactantscould be employed to produce products comparable to those hereindescribed. We have found the contrary to be true. For instance, we areaware that there are a variety of other high molal dicarboxy acids, suchas sebacic acid, analogues Other classes include dimers of abietic acid,etc. Acetalized ricinoleic acid is an additional example. Diels-Alderand Clocker adducts represent another type, particularly when derivedfrom maleic anhydride, etc. We have not found such particular productscould be substituted for the reactants herein described, andparticularly, the dimeric acids indicated in detail. Similarly, otheramines bearing a-superficial resemblance to the polymeric productsherein described are known. One class is obtained by the polymerizationof oxyethylated polyalky lene amines, particularly those having four tofive amino nitrogen atoms. We have not found such products to serve assatisfactory reactants.

The new materials or compositions of matter herein described are usefulas wetting, detergent and leveling agents in the laundry, textile, anddyeing industries; as wetting agents and detergents in the acid washingof fruit, in the acid washing of building stone and brick; as a wettingagent and spreader in the application of asphalt in road building andthe like, as a constituent of soldering flux preparations; as aflotation reagent in the flotation separation of various minerals; forfloculation and. coagulation of various aqueous suspensions containingnegatively charged particles, such as sewage, coal washing Waste water,and various trade wastes, and the like; as germicides, insecticides,emulsifiers for cosmetics, spray oils, water-repellent textile finish,etc. These uses are by no means exhaustive, as far as industrialapplication goes, although the most important use of our new material isas a demulsifier for water-in-oil emulsions, and more specifically,emulsions of water or brine in crude petroleum.

We have found that the chemical compounds herein described, which areparticularly desirable for use as demulsifiers, may also be used as abreak inducer in doctor treatment of the kind intended to sweetengasoline. (See U. S. Patent No. 2,157,223, dated May 9, 1939, toSutton.)

Chemical compounds of'the kind herein described are also of value assurface tension depressants in the acidization of calcareous oilbearingstrata by means of strong mineral acid, such as hydrochloric acid.Similarly, some members are effective as surface tension depressants orwetting agents in the flooding of exhausted oil-bearing strata.

As to using compounds of the kind herein described as flooding agentsfor recovering oil from subterranean strata, reference is made to theprocedure described in detail in U. S. Patent No. 2,226,119, datedDecember 24, 1940, to De Groote & Keiser. As to using compounds of thekind herein described as demulsifiers, or in particular as surfacetension depressants, in combination with mineral acid for acidization ofoil-bearing strata, reference is made to U. S. Patent No. 2,233,383,dated February 25, 1941, to De Groote & Keiser.

The new compounds herein described are of utility, not only for thepurposes specifically enumerated in detail, but they also findapplication in various other industries, processes, and for various useswhere wetting agents of the conventional type are used. As to some ofsuch additional uses which are well known, see The expanding applicationof wetting agents, Chemical Industries, volume 48, page 324. (1941).

Another use for the compounds herein contemplated is in the preventionof landslides, as described in U. S. Patent No, 2,348,458, dated May 9,1944, to Endersby.

It may be well to note that polymerization of polyene acids is notlimited to the esters, but that the acids per so may be polymerized.This fact is noted, forexample, in the aforementioned Johnson U. S.Patent No. 2,347,562,

Insofar that the acid employed is dibasic, and since the oxyalkylatedheat-polymerized condensate is very apt to be polyhydroxylated, it isobvious that resinification takes place to a greater or lesser degree,and particularly in such instance is where etherification is caused totake place along with esterification. This fact, added to What has beenpointed out previously, emphasizes the difficulty of attempting todepict the final product by any approximation of a structural formula.

Having thus described our invention, what We claim as new and desire tosecure by Letters Patent is:

1. A basic aminoalcohol mono-ester, in which the aminoalcohol radical isthat of an oxyalkylated heat-polymerized aminoalcohol, whichheatpolymerized aminoalcohol is surface-active and additionally is theresultant of the heat polymerization in the presence of an alkalinecatalyst to at least the tetrameric state of the nonsurfaceactivemonomer [noarommln N l]n wherein GR is an alkylene oxide radical having4 carbon atoms or less; R1 is a member of the class consisting ofhydrogen atoms and alkyl radicals having 6 carbon atoms or less; mrepresents a numeral varying from to 3; n represents a numeral varyingfrom 2 to 3; and n represents a numeral varying from 0 to 1, with theproviso that n pius n equals 3; the radical introduced by oxyalkylationbeing a repetitious oxyalkylene radical, in which the units have 4carbon atoms or less; the number of said units introduced peraminoalcohol polymer being not in excess of the molal ratio of 15 to l;and the acidic radical of said aminoalcohol ester being the dimerobtained by polymerization at elevated temperature of a substanceselected from the group consisting of polyene higher fatty acids andtheir methyl and ethyl alcohol esters.

2. An aminoalcohol ester, as described in claim 1, wherein n is zero.

3. An aminoalcohol ester, as described in claim 1, wherein n is zero,and m is zero.

4. An aminoalcohol ester, as described in claim 1, wherein n is zero, mis zero, and OR is the ethylene oxide radical.

5. An aminoalcohol ester, as described in claim 1, wherein n is zero, mis zero, OR and every alkylene oxide radical is the ethylene oxideradical, and the monomeric polyene fatty acid radical has 18 carbonatoms.

6. An aminoalcohol ester, as described in claim 1, wherein n is zero, mis zero, OB and every alkylene oxide radical is the ethylene oxideradical, the monomeric polyene fatty acid radical has 18 carbon atoms,and the heat-polymerized amino-alcohol prior to oxyethylationrepresenting the range of the tetrameric state through the hexamericstate.

7. An aminoalcohol ester, as described in claim 1, wherein n is zero, inis zero, OR and every alkylene oxide radical in the ethylene oxideradical, the monomeric polyene fatty acid radical has 18 carbon atoms,and the heat-polymerized aminoalcohol prior to oxyethylationrepresenting the range of the heptameric state through the nonamericstate.

8. An aminoalcohol ester, as described in claim 1, wherein n is Zero, mis zero, OR and every alkylene radical is the ethylene oxide radical,the monomeric polyene fatty acid radical has 18 carbon atoms, and theheat-polymerized aminoalcohol prior to oxyethylation representing therange of the decameric state through the dodecameric state.

MELVIN DE GROOTE. BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS

